JPS59149360A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To enhance color purity by incorporating monodispersed silver halide grains and a compd. capable of releasing a development inhibitor upon reacting with the oxidized product of an essential color developing agent, and producing a mobile reaction product in a photosensitive silver halide emulsion layer. CONSTITUTION:A photosensitive silver halide emulsion layer in a silver halide photosensitive material obtained by forming the photosensitive silver halide emulsion layer on a suport incorporates monodispersed silver halide grains and a compd. capable of releasing a development inhibitor upon reacting with the oxidized product of an essential color developing agent and capable of producing a mobile reaction product. Said compds. DIR and T-DIR are represented by formulae A-Z, A-TIME-Z, respectively, in which A is a group capable of being released from said compd. after reacting with the oxidized essential color developing agent and producing a mobile reaction product, and TIME is a timing group capable of releasing Z after being released from said compd. together with Z by the reaction of A with said oxidized agent, and Z is a group having development inhibiting action.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Sedentary Use) The present invention relates to silver halogen photographic A light-sensitive materials, and particularly to halogenated silver multilayer color photosensitive materials. In more detail, after image exposure, the presence of kabucy, which reacts with the oxidized form of the developing agent to form a dye, is developed using an aromatic primary amine color-forming developing agent, and the layer in which the photosensitive halogenated pot was present. This invention relates to a silver-free saponified multi-color photosensitive material of the type in which a silver image and a dye image are formed, and then only one silver image is removed to utilize only one dye image.

(Prior art) In multilayer color photography, the q4 character of each image is +! iced. One of the reasons is that the outline of the image is clear and detailed images are depicted without blurring, that is, the sharpness is good.

Another property is that when one color-sensitive layer forms a dye image,
The other color-sensitive layers are not colored by the oxidized product of the color-forming developing agent produced thereby, and the color is not muddy, that is, the color is 8 purity.

Another reason is that the formed dye image has good stability over time.

In response to these demands, various improvements have been made to silver halide photographic photosensitive materials, particularly silver halide multilayer color photographic materials.

The sharpness of nil 14e is mainly studied from the viewpoint of preventing optical scattering in the IG optical phase material and improving the adjacency effect during development. Selection of low-volume silver particles, reduction of losses, and selection of silver particles as a light source.
Methods such as making thin films of photosensitive and non-photosensitive J and i true functional JFII have been adopted.

Although the above-mentioned scientific method yielded even better results, this method alone did not improve photographic performance or the production of light-sensitive phase materials.
There were times when I was at odds with my responsibility, and I reached my own limits and was unable to achieve sufficient results.

On the other hand, regarding the adjacency effect during development, we will also discuss the difference between sharpness and color purity.Firstly, we will discuss the effects of color purity and other inhibitory substances released during development. From the viewpoint of the concentration gradient, countermeasures have been attempted from the perspective of visual and operational aspects, such as dilution due to development or weak stirring during development, but they have been difficult to solve due to the complexity of image carrying operations and uncertainty in setting conditions. It is easy to have problems with performance and it is difficult to reach satisfactory results.1. It was c.

Secondly, a method of actively suppressing the adjacency effect was investigated by adding a compound that reacts with the oxidized form of colored dust 1 and releases an on-image suppressor to the photosensitive material. Moreover, this compound has been extensively explored.

A compound that releases a development inhibitor by reacting with the oxidized form of a color developing agent.
Compounds (hereinafter referred to as D
IR Kagler) or U.S. special W [No. 3,632
, 345, there are known compounds (hereinafter referred to as F, DIR substances) that release development inhibitors and do not form dyes by cuff linking with oxidized forms of color developing agents (hereinafter referred to as DIR substances). DIR couplers and DIR substances are collectively referred to as DIR compounds).

The characteristics of these DIR compounds are that they react with the oxidized product of the color developing agent and #L image side developer lji!
, located at the point where it is exposed to radiation.

Furthermore, JP-A-54-145135 discloses a DIR compound that reacts with an oxidized color developing agent to release a development inhibitor through an intramolecular nucleophilic substitution reaction.
No. 114946 discloses that D!11L molecules are transferred along the conjugated chain to indirectly release the tljll agent. R compounds are listed at ℃・ru. Compound of Kosai 1 et al.&1. The reaction with the color-forming color-developing agent is characterized by the intermittent release of the development inhibitor due to the secondary reaction caused by the reaction (hereinafter, DIR adducts having this characteristic are referred to as ”-DIR compounds).

These compounds form dyes, which are alkali-insoluble products, by ashing with the oxidized product of the color developing agent, and remain during photographic searches. 7. True photosensitive paulownia materials that do not use Gazuka cause color turbidity when used in layers containing cuffers with different hues, which is preferable in terms of color reproduction. It also has the major drawback of being ugly. Another drawback is that they are not suitable for use in photographic systems that involve diffusion transfer of dye images formed by reaction with oxidized color developing agents.

On the other hand, as a component of a photographic cuffler, a compound that produces a colorless reaction product by reaction with an oxidized form of a color developing agent is not advantageous because it does not have the aforementioned problem of color turbidity in light-sensitive materials. However, the reactivity with the oxidized product of the color developing agent is poor, and in addition, the retention properties of the compound are poor. )
Ta.

By using a DIR compound, the granularity can be improved by 1μ, but it is not very effective in improving the color purity.Also, T-DI
With the R compound, Hu, 1'4. It is suppressed at 1-1 at a certain distance M from the I-Loken particle.
It is possible to develop the effect of the drug (if), °C.
・In the so-called interlayer effect, there is a 1-ki r-fold (Jf', I-junction,
It improves by 1u to some extent. Also, based on the ll# contact effect) there is also bamboo sharpness. 3: Improved strength, color purity, and oatiness. The rewriting effect is small. m by using tR compounds or/and T-DIR compounds
Improvements in sharpness, graininess, and color purity, as well as wide lag and cheese formation, are still not sufficient.

The adjacency effect measurement during development is based on MTF Moderation Transfer Fancy 7 (Modulation Transfer P), which is said to be correlated with the psychological image sharpness evaluation in human 1N and relaxation.
1 due to the low frequency band of the spatial frequency of
However, there is a point where it is more difficult to implement immediately.

In addition, the characteristics required for a four-layer silver halide color photographic light-sensitive phase material include:
Regarding stability over time, it is an essential characteristic for image recording preservation, and it is also a multi-layered, multi-layer structure that has been added to meet the demands of photosensitive materials from other photographic or biological subjects. It is believed that the stability of the cooling agent over time is somehow impaired by the various layers of compounds remaining in the cooling agent, and although improvements have been attempted, there is still sufficient J & I have come to honor the vermilion (・buko℃・.

(Object 1 of the invention) All AI) In connection with the Hfi problem, the first object of the invention is
The purpose of &J, l! If sharpness and derivatively good color purity, especially in the low frequency band (0 to 3) of the same frequency as M゛rF.
211 songs/Ki) has been improved.
・Providing multi-layer color photographic photosensitive materials.

The second objective Fl'J is to provide a multi-layer color photographic material in which the stability of dye images formed by color development is improved.

(Creation of the invention) In accordance with the above-mentioned purpose, the above-mentioned DIR and T-DIR are mainly influenced by the silver halide grains as optical factors and the adjacency effect at the time of tax image. ℃ for the compound, and the silver halide particles described above, color development 81! The reaction efficiency between the herbal drug and the DIR or T-DIR compound and the appropriate ratio for the inverse reaction are carefully investigated.
As a result of research, it was found that in a halogenated photosensitive photosensitive material that forms at least one photosensitive silver halide emulsion layer on a support, a substantially monodisperse In the reaction between the silver halide grains and the color developing main oxidized mulberry, a development inhibitor is released and a reaction product to be transferred is produced. The halogenated LC photosensitive material of the present invention was constructed by selectively combining and containing DIR and/or T-DIR compounds which exhibit high reaction efficiency due to their synergistic effect and require only a small amount of food.

Due to the MtJ structure, there is an adjacent effect, and therefore, the river: plane storm is fresh, the same as above, θ1 (chemically, the color purity is good, and the DIR conversion property, etc., is reduced, and the photosensitive paulownia of the reaction and product is The stability of the inner cord image, which was surprisingly formed due to the outflow of the stratum corneum, was said to be good for 1 second.

Also +iii M+: A needle that feels like a halokun! In the emulsion layer (the bulging adjacent effect can be applied to each layer of a multilayer light-sensitive material without any problem), the purpose of this defense and -3
There are 141 silver halide color photosensitive phase materials.

Next, the DIR and T-DIR compounds which are used in the present invention and which release a development inhibitor and produce a mobile reaction product upon reaction with the oxidized product of the color developing agent will be described.

General formula (+1 -Z General formula 1ll A -TIME -Z Here, A is released from the compound represented by the general formula (1) or represents a group capable of forming a mobile reaction product,
TIME&'jThe front A represents a timing group that can be released from the compound represented by the general formula ffl+ together with 2 by reacting with the oxidized product of the color-forming main agent, and 2 represents a timing group that can be released from the compound represented by the general formula ffl+. Represents a group that has an inhibitory effect.

The present invention will now be described in detail.

In the general formula (1) or flit representing the compound according to the present invention, A is desorbed from the compound represented by the previous iE2 general formula (RI or +II) when it reacts with the oxidized product of the color developing main mulberry as described above, Mobility Zunawa Arca +)
It is a group that forms a 5sm reaction product, and specifically, it is a photographic coupler residue.

Therefore, in the present invention, the above A is f of the color forming type 1 image agent.
Caffler residues, etc., which form an alkali+7oJ bath-like reaction product when eliminated from the compound represented by the above general formula by nn outer reaction, are absorbed.

The above-mentioned cuffler residues that can also be used in the present invention can include those having a volume of cuffler N nucleus, for example, in yellow cuffler, benzoylacetanilide thread compound or pivaloylacetanilide thread compound. Open-chain ketomethylene compounds such as cyano or bivaloylacetanilide thread compounds are used for 41, and for macenta couplers, hyrasolone thread compounds, intanolone thread compounds, pyrazolotriazole compounds, etc. can be used, and for cyan cufflers. In that case, it is possible to weave unphenolized specialties, naphthol thread compounds, etc.

In the present invention, even if an inverted coupler residue is used, the reaction product formed when it reacts with the oxidized product of the color former and image agent must not have bath properties against alkali. , in order to impart such properties to the above reaction product,! If at least one molecule of the oxidized product of the lir + kaffler residue or the oxidized bioactive drug must have an alkali IJ 'i'J M group, 1. (According to the present invention, at 5°C, an alkali-soluble thread is added to the photographic coupler residue shown in A above.) Alkaline IJ OJ solubilizing η and Jul 1 may also be used, and both may be provided with an alkali saponifying group. 1.011
Go'IMF: represented by the general formula +fi+ is,
l: As mentioned in III, in the coupling reaction according to the above 11, 2 of the general formula tn) and r (r) are eliminated from the compound of the general formula (11), and then 2 is released and 1 (! represents a timing base.

An example of such a timing group is analogy C:
6837, which releases a group having an IJt image suppressing effect by an intramolecular nucleophilic substitution reaction, and JP-A-56-114946,
It is possible to prevent the release of a group having a development inhibiting effect through a chain transfer reaction along a conjugated chain, as described in 81 publications such as JP-A No. 57-IF14234.

The above TIME groups useful in the present invention include, but are not limited to, the following general formulas (al, fb) and (cl). Shrimp type (al It.

t2 Here, X represents the Noe atom II+ necessary to form a benzene salt or a p7talene ring, Y represents 10-23 ■ -s-, -N-, and the general formula (III
It also binds to the coupling position of the compound shown by l(
, , lζ2itiyohi lL3 are each water-based yit child,
Represents an argyl group or an aryl group.

R.

In addition, -C- is substituted at the Zult position or the 2nd para position with respect to Y, and the other is bonded to the betero atom of the group represented by 2.

Here, Y, R, and R2 have the same meanings as in the general formula (a) above. R is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or an initial f-broken group; Represents an alkoxy group, an aminoacylamido group, a sulponamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, or cyano.

The manner of bonding of this timing group to A and 2 shown in the general formula tn) is the same as in the case of the general formula (al).

General formula (cl -Nu-XI-E- Here, Nu is a nucleophilic group which also cures a mono-enriched 9-rich oxygen, chlorine or nitrogen atom, and the coupling position to in the general formula (Il) is E is an insufficient carbonyl group, thiocarbonyl group, phosphinyl group,
Alternatively, it is an electrophilic group having a thiophosphinyl group, and is bonded to the 2 hetero atom in the general formula +Ill. Xl has the above-mentioned Nu group and E group sterically related to each other, and the general formula
j, = j: l yo 5 molecule inner edge round shape 1 with the formation of ji, j
The above general formula ([
The above general formula (1
1 or 1, Z represents a group that has a development inhibiting effect as described in AiJ, and is a group that can be used as a permanent pattern in the photograph. A typical example of a compound having such a group that inhibits development is U.S. Patent No. 227. fi54
No. 3, 384, 657, No. 3.615,
No. 506, No. 3, No. 617, No. 291, No. 3.7
No. 33,201 and British Special Wt No. 1.45 (1,47
9) a) Mercaftotetrazole, selenotetrazole, merkaftobenzothiazole, selenobenzothiazole, merkaftobenzokylyzole, selenobenzoxazole, merka7topene imitazole, seleno Benzothiazole, penzotrianol, benzodiazole size ◇. L-hyodide 1. "
To be angry.

It is already clear from 7J to 5 that this compound is not only highly reactive with the oxidized form of color developing agent, but also has a viscous binding property of the reaction. The reaction product is given alkali solubility and can be flushed out of photographic additives, so it can be used in a wider range of applications than the compounds produced in the prior art. It is.

Hereinafter, specific representative rows of compounds related to the present invention are listed below.
The present invention is not limited to these.

(compound row) 8U2 '1°--2 02 'l' -3 'l' -4 b) p -5 Sχ ’l”　　　-6 OOH 8o3)1 T-8T U, H, (1so) -9 o2 ’[’　　　-1/1 'I' -15 B, r T -Hi −17 18 T -2F+ T-21 'l' -22 N(12 U, H, (ts 'r　-blade +j00+8H.

? 10° -40 1+14 'l'5tノ 1' -51 C) G NO+ -52 Lllll.

1'-5,8, horoscope issue 101° e219 T-5b n 11 '1' -5+) (111 1]-1 -2 -4 [11 1--5) (:! 1)-6 D-8F+1+,,l　I -9 1( 113 IJ-12 D-13 [)H 1) -14 -15 r D -1tj 1) -17 1) -19 r 1) -Ka 1)-21 D-31 ]) −32 1,1-4t+ H 1) -5(J O)( 1) -51c)s l,) -5: Movie.

■■)-6 [11-1 In the present invention, the DIR compound or/and the T-DIR compound contain silver halide grains having substantially divisive properties.
It may be contained in at least one of the silver halide emulsion layers contained therein. For example, when applied to a normal multilayer color photographic light-sensitive material having a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer, it may be contained in one of these layers or 2111 or more, but at least green It is preferable to include it in the sensitive emulsion layer. In addition, when an emulsion layer having a certain color sensitivity is composed of vI layers that limit the sensitivity, it may be contained in one or more of those layers, but it may be contained in at least a low-sensitivity emulsion layer. It is preferable to do so.

In the color photographic material according to the present invention, the total amount of the DIR compound or /' and T-DIR compound is preferably in the range of 0.0005 to 0.05 mol per mol of silver halide in the emulsion. Particularly preferably 0.001 to 0.
The range is 0.01 mole.

The color developing agent used in the present invention may be any color developing agent used for developing silver halide color photographic light-sensitive materials. A primary amine color developing agent can be used.

The coupler used in the color photographic light-sensitive material of the present invention, that is, the compound that reacts with the oxide of the developing agent to form a dye, is a non-diffusible compound that has a hydrophobic group called a ballast group in the molecule. Desirable 0 couplers may be either 4-equivalent or 2-equivalent to silver ions.

Also, depending on the form of the coupler (-), it may be of low molecular weight, or it may be a so-called polymeric coupler (10).As the yellow coupler, a known open-chain ketomethylene thread coupler can be used. Ilylacetanilide compounds are useful.

As the magenta coupler, a pyrazolone compound, an ingzolone compound, a cyanoacetyl compound, and a cyan coupler such as C is a phenol compound, a naphthol compound IL, etc. can be used.

These couplers generally contain 2
XlO-" mole to 5XlO-'-!-l, preferably 1
x10-2 mol-5X10=mol added.

In the present invention, which coupler is added to which silver halide emulsion layer in a multilayer color photographic light-sensitive material is not necessarily limited, but a yellow coupler is added to a blue-sensitive silver halide emulsion layer, and a yellow coupler is added to a green-sensitive silver halide light-sensitive layer. A magenta coupler is used in the red-sensitive silver halide emulsion layer and a cyan coupler is used in the red-sensitive silver halide emulsion layer, or a magenta coupler is used in the blue-sensitive silver halide emulsion layer and a cyan coupler is used in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. It is preferred to use a yellow coupler on one side and a cyan coupler on the other.

Although there are various methods for incorporating the DIR compound and/or T-DIR compound or coupler according to the present invention into a light-sensitive material, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known for a long time, and the latex dispersion method and its effects are described in Japanese Patent Application Laid-open No. 49-74538\No. 51-59943, No. 54
-32552 Publications and Research Disclosure 5
August 1976, AI4, 850, pages 77-79.

Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetate, diethyl methacrylate, 2
-(methacryloyloxy)ethyltrimethylammonium sulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2- Acrylamide-2
- Homopolymers, copolymers and terpolymers of common monomers such as methylpropanesulfonic acid. As the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied. The DIR compound or/and T-DIR compound used in the present invention is
It may be dispersed simultaneously with other couplers, or may be dispersed separately and added independently.

Further, by interposing one or more scavengers at appropriate positions in the constituent layers of the photosensitive material, the layer or unit layer affected by the development inhibitor can be controlled.

The silver halide used in the Asahi color photographic light-sensitive material of the present invention preferably consists essentially of silver iodobromide with a content of less than 12 mol %, where "substantially" means silver halide produced. This shows that even though the silver iodide produced during the process contains some silver iodobromide grains exceeding 12 mol %, the average thereof is less than 12 mol %. In the present invention, a more preferable mol% of ash dust is 2 to 9 mol%. The silver iodobromide emulsion may have large grains or small grains, but is substantially a monodisperse emulsion.

In the present invention, a monodisperse emulsion is one in which the standard deviation S defined by the following formula is divided by the average grain size 〒 and the value is 0.20 or less. The grain size is the diameter 1 in the case of spherical silver halide grains, and the average value of the diameter when the projected image is converted into a circular image of the same area in the case of grains with shapes other than spherical. When the individual grain size is rl and the number is nl, 〒 is defined by the following formula.

The emulsion can be a negative emulsion or a direct positive emulsion. They are mainly surface latent image type emulsions that form latent images on the surface of silver halide grains, internal latent image type emulsions that form latent images inside silver halide grains, or surface latent image type emulsions and internal latent image type emulsions. A mixture of can be used.

The silver halide grains used in the silver halide color photographic light-sensitive material according to the present invention may be so-called twin crystals having irregular shapes such as spherical or plate-like, or cubic, octahedral, or tetradecahedral. It may be a regular shape, but the latter is more preferable, and regular shapes, irregular shapes, and the like can also be mixed with each other.

The silver halide grains used in the silver halide color photographic light-sensitive material according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method.

Alternatively, for example, a method may be used in which seed particles are produced using an acid method and then grown using an ammonia method, which has a faster growth rate, to grow to a predetermined size. (b) When growing silver halide grains, control the pH, PAg, etc. in the reaction vessel, and adjust the amount to match the growth rate of silver halide grains, as described in JP-A No. 54-48521, for example. It is desirable to simultaneously implant and mix silver ions and halide ions.

These silver halides include: activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, polyamines. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-oh, rosulfobenzothiazoniochloride, etc., or water-soluble compounds such as ruthenium 1 palladium, platinum, rhodium, iridium, etc. Sensitizing agents such as ammonium chloroparadate, potassium chloroaurate, and sodium chlorovaladate (these types can act as sensitizers or fog suppressants depending on the amount) ): may be chemically sensitized either alone or in appropriate combination (for example, a combination of metal sensitization and a sulfur sensitizer, a combination of metal sensitization and a selenium sensitizer, etc.). .

Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using an optical sensitizer such as a cyanine dye such as a zeromethine color chart, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye. Alternatively, optical sensitization can be achieved in combination (for example, superchromatic sensitization).

Other specific configurations of the silver halide color photographic light-sensitive material according to the present invention can be found in Research Φ Disclosure A.
18431 can be applied.

The silver halide color photographic light-sensitive material according to the present invention is usually prepared by successively red-sensitive halogenation on the support.

A silver emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer are provided.

In the present invention, each light-sensitive silver halide emulsion layer may have a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. In this case, the combination of the present invention, that is, the combination of a monodisperse silver halide emulsion and a T-DIR and/or DIR according to the present invention, may be a combination of a monodisperse silver halide emulsion and a T-DIR and/or DIR according to the present invention. It may be applied to silver halide emulsion counterfeiting, but it may be applied at least to silver halide emulsion FIJ, which has lower photosensitivity.

As the binder for the silver halide emulsion according to the present invention,
Various hydrophilic colloids including gelatin are used. In this case, gelatin includes not only gelatin but also derivative gelatin, and derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and incyanate, or a reaction product of gelatin and an active halogen atom. This includes reaction products with compounds having the above.

In addition to the above-mentioned ordinary photographic gelatin and derivative gelatin, if necessary, colloidal Alepmin 1 agar,
gum arabic, dextran 1-alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 19-26%, polyacrylamide, imidized polyacrylamide, casein, e.g. vinyl alcohol-vinyl cyanoacetate copolymer. Vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as rimers, polyvinyl alcohol-borivinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups. , polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. The silver halide emulsion according to the present invention can contain various commonly used additives depending on the purpose.

Examples of these additives include stabilizers and antifoggants such as azaindenes, triazoles, tetrazo-1s, imidazolium salts, tetrazolium salts, and polyhydroxy compounds; , vinyl alcohol, acrylic, a!
Hardening agents such as levodiimide thread, maleimide series, methanosphlephon ester series, and triazine series; Development accelerators such as benzyl alcohol lyoxyethylene thread compounds; Chroman series, coumaran series, bisphenol series, and blood! Ester-based image stabilizers; wax, tux, glycerides of higher fatty acids, higher alcohol esters of higher fatty acids As activators, coating aids, permeability improvers for processing solutions, etc., antifoaming agents, and various photosensitive materials. Various types of anionic, cationic, nonionic, or amphoteric materials can be used as materials for controlling the physical properties of. As antistatic agents, diacetylcellulose, styrene/burf lheoloalkylsodium maleate copolymer, alkali salts of reaction products of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. be. Examples of matte shavings include polymethyl methacrylate/polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. The latex added to improve the physical properties of the film may be a copolymer of 1-vinyl acrylate or another monomer having an ethylene group. Examples of gelatin plasticizers include glycerin and glycol thread compounds, and examples of thickeners include styrene-sodium maleate copolymers, alkyl vinyl ether-maleic acid copolymers, and the like.

Examples of the support according to the invention include baryta paper.
Polyethylene coated paper, polypropylene synthetic paper, glass,
Examples include cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, and polystyrene.1 These supports are appropriately selected depending on the purpose of use.

These supports are subjected to undercoat processing, if necessary.

Coating methods used in the present invention include dip coating, air knife coating, curtain coating, or U.S. Pat.
Various coating methods may be mentioned, including extrusion coating using a hopper of the type described in No. 681.294.

Optionally, bilayers or multiple layers may be used in U.S. Patent No. 2,761,7.
91 and British Patent No. 837,095. The silver halide color photographic light-sensitive material according to the present invention can be coated simultaneously by the method described in No. 91 and British Patent No. 837,095. It includes all kinds of silver 10 genide color photographic light-sensitive materials.

The color developing agent used in the present invention is an aromatic primary amine compound, and particularly preferably a p-phenylenediamine type developing agent, such as 4-amino-N, N-diethylaniline, 3-methyl-4-7 Mi/-NIN-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline 1,3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-methoxyethylaniline, 3-β-
Methanesulfonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N- β-methoxyethylaniline, 3-acetamido-4-ami/-N,N-diethylaniline, 4-amino-N,N-dimethylaniline, N-ethyl-N-β-[β-(β-methoxyethoxy) [ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoanis/and their salts, such as sulfur salts, hydrochlorides, These include sulfites and p-toluenesulfonic acid.

Photographic additives used in these color developing solutions include alkaline agents (for example, alkali metal or ammonium hydroxides, carbonates, 1 phosphorus!), pH adjustment or buffering agents (for example, acetic acid, boric acid, etc.). weak acids and bases and their salts), development accelerators (e.g. pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate-polyethylene glycol condensates and their derivatives, polythioethers and other 7-ionic compounds, Polymer compounds containing sulfide esters, other pyridine, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc.) ＼ Capri inhibitors (e.g. alkali bromide, alkali iodide, nitrobenzimidazole, etc.)
5-Methylbenzo) leaf'/'-l, 1-phenyl-5-mercaftotetrazole, compounds for rapid processing liquids, nitrobenzoic acid, benzothiazolium derivatives, phenazine-N-oxides, stain or sludge inhibitors , multilayer effect accelerators, and preservatives (for example, sulfites, acid sulfites, hydroxylamine hydrochloride 1-form sulfide, alkanolamine sulfide adducts, etc.).

After color development, the photographic emulsion layer is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment or may be performed separately. Bleach agents include iron (■) and cobalt (
Compounds of polyvalent metals such as (■), chromium (■), and copper ([), peracids, quinones, and nitroso compounds are used. For example, ferriciano compounds, deuterium salts, iron (
[[) or organic complex salts of cobalt(III), such as ethylenediami/tetraacetic acid, nitrilotriacetic acid, 1.5-
Amino/polycarboxylic acids such as diamino-2-propatoltetraacetic acid, complex salts of organic acids such as citric acid, tartaric acid, and malic acid, persulfates, permanganates, nitrosophenols, and the like can be used. Among these, potassium ferricyanide, ethylenediaminetetraacetate iron(l[) sodium and ethylenediaminetetraacetate taron(III)
Ammonium is particularly useful. Iron(III) ethylenediaminetetraacetic acid complex salts are useful both in stand-alone bleaching solutions and in -bath bleaching solutions.

For bleaching or bleach-fixing solutions, U.S. Patent No. 3,042.5
No. 20, No. 3,241,966, Special Publication No. 45-850
In addition to the bleach accelerators described in Japanese Patent Publication No. 6, No. 45-8836, and the thiol compounds described in Japanese Patent Publication No. 53-65732, rice ear additives can also be added.

(Examples) The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Note that the sharpness improvement effect was detected by determining the MTF and comparing the magnitude of the MTF at a spatial frequency of 10 lines/1111.

Next, the method for preparing the emulsion used in the examples is shown below. Then, Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and magnesium sulfate aqueous solution were added, precipitate #1 was desalted, gelatin was added, and PAg
7.8, an emulsion with a pH of 6.0 was obtained. Furthermore, add sodium thiosulfate J, chloroauric acid and rhodan ammonium,
4-hydroxy-
6-methyl-1,3゜3a,7-chitrazaindene and 6
- Nitrobenzimidazole was added, and gelatin was further added to obtain a polydisperse silver iodobromide emulsion. Here, by changing the alkali halide composition, the silver iodide mol% was changed by 1, and by changing the addition time of ammoniacal silver nitrate and aqueous alkali halide solution, the average particle size and particle size distribution were changed.

[Preparation of monodispersed emulsion]

While keeping the PAg in the reaction pot constant, add an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution in proportion to the increase in surface area during grain growth into a reaction pot containing potassium iodide and gelatin aqueous solution in advance. did. Next, a Demol N aqueous solution manufactured by Kao Atlas Co., Ltd. and a magnesium sulfate aqueous solution were added to perform precipitation and desalting, and gelatin was added.
An emulsion with pAg 7.8% and pH 6.0 was obtained. Furthermore, sodium thiosulfate, chloroauric acid, and rhodan ammonium were added, chemical ripening was performed, and 4-hydroxy-6-methyl-
1,3°3a,7-titrazaindene and 6-nitrobenzimidazole were added, and then gelatin was added to obtain a monodisperse silver iodobromide emulsion. Here, by changing the ratio of potassium iodide and potassium bromide, the silver iodide mol% is changed,
The crystal habit was changed by changing the pjkg value, which should be kept constant, in the reaction vessel. The particle size was also changed by changing the amounts of ammoniacal silver nitrate and potassium halide.

Example 1 1-(2,,4,6-)lichlorophenyl)-3-(3-(2,4-di-t-amylphenoxyacetamide)-5-pyrazolone 50y as magenta coupler and The DIR compounds according to the present invention shown and the following comparison D
IR compound with ethyl vinegar 200 m! and tricresyl phosph' --) 100 #Ij, and added to an aqueous gelatin solution containing Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and emulsified and dispersed in a colloid mill. This dispersion was then added to a green-sensitive silver bromide emulsion as shown in Table 1 to form a silver amount of 2.
．． It was coated and dried so that it became 01//rrl.

Each of the samples 1 to 13 obtained in this way was subjected to contact exposure using a transparent rectangular wave chart or wedge, and line image exposure with a width of 4 and a width of 10 μm using a software Xi, and then subjected to the following processing steps. A sample with a dye image was obtained.

Comparative DIR Compound (1) Comparative DIR Compound (2) Treatment Step (Warm 38'C) Treatment Time The composition of the treatment liquid used in each treatment step is as follows.

[Color developer]

[Bleach solution] [Fixer] [Stabilizing solution] Soft XI! The density of the sample exposed to N light was measured by scanning with a microdensitometer using green light. 10μ
The density of the line image of m is 9 degrees, and the density of the line image of 033 mm is p,
CDI' - Dl') /D1' is 0 which represents the magnitude of the edge effect of the sample when observed with green light.
In other words, it can be said that the larger the value of D1'N/DI', the greater the edge effect when observed with green light.The values of D1'-rf)/D,' of each sample are shown in Table 1. About this &i [Color Photography Developer Release (DIR)
1 coupler” (Photographic Science and Engineering Link, pp. 78-79, Vol.
13, 42 March-April (1969)) with a detailed explanation.

A description of the apparatus used to produce X-ray images is ``Apparatus J for the formation of clear photographic images by means of X-rays''.
for Maklng 5harp Photogra
phlo Imagea vrlth:2. X-Ray
s) The Revue Ope Scientific Instruments/) Vol, 38 Graves 11. No. 1619~
No. 1622, Nov. 1967.

In addition, the light resistance, heat resistance, and moisture resistance of color chart images were investigated using samples obtained by wedge exposure.

The results obtained are shown in Table 1. In addition, in the table, the light resistance is
Each of the obtained images was exposed using a xenon fade meter, and the residual density after exposure for 300 hours was expressed with the density before exposure being 100. Moisture resistance was expressed as the residual concentration after storage for 3 weeks at ω° C. and 70% relative humidity, with the concentration before the test being 100. Furthermore, heat resistance was determined by measuring the residual concentration of sample 1 after storage at 77°C for 3 weeks, as shown in Table 1 of the test.
Looking at the results of ~6, when the DIR compound of the present invention is used in a polydisperse emulsion system, the adjacent effect during development is as follows:
Although some effect was observed compared to the comparative DIR compound, the storage stability of the dye image was poor (not improved).

Furthermore, in the monodisperse emulsion systems of Samples 7 and 8, both the adjacency effect and the storage stability of dye images are not significantly different from those of Samples 1 to 6. However, Samples 7 to 13 surprisingly had greatly improved adjacency effects during development and storage stability of dye images, and were coated sequentially from the 1st layer to the 13th layer below to form a multilayer coating. Color negative photosensitive materials (samples 14 to 24) were prepared.

1st layer: Halley sheen prevention layer A gelatin aqueous solution containing black colloidal silver is added to the silver 0.3j! /
It was applied so that it was 1 m1.

2nd layer: Intermediate layer An aqueous gelatin solution was coated to a dry film thickness of 1.0 μm.

3rd layer: Red-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6μ, silver iodobromide emulsion containing 4 mol% silver iodide, average grain size 0.3μ, Silver iodide 4 mol%
A silver iodobromide emulsion (mixed in a ratio of 2:l) with 4:1) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-di (3-Sulfopropyl)-4゜5,4: 5'-dibenzothiacarbocyanine hydroxide; anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl)thiacarbocyanine hydroxy and anhydrous 2-(2-((5-
After adding chloro-3-ethyl-2(3H)-penzothiazoliden)methyl 1-1-butenyl-5-chloro-3-(4-sulfobutyl)pendioquinazolium, 4-
A red-sensitive, low-sensitivity emulsion was prepared by adding hydroxy-6-methyl-1,3,3a, 1.0 # of 7-tetrazine, and 20.0 # of 1-7 enyl-5-mercaptotetrazole. Furthermore, l-hydroxy-N-(4-(2,4-sheet t-
(amylphenoxy)butyl] 5911 Also, add 0.5.9 d of dodecyl galley'), 1 tricresyl phosphny) 65 JBl', dissolve the mixture with heating and 136 d of ethyl acetate, and dissolve 5.9 d of sodium triisopropylnaphthalene sulfonate.
A red-sensitive, low-sensitivity emulsion was prepared by adding the dispersion emulsified and dispersed in a colloid mill to 550 volumes of a 7.5% gelatin solution containing Y, and the coated silver amount was 2.01//rt? It was applied so that ()160g per mole of silver 10genide
Contains gelatin. ) No. 411: Red-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide) is chemically sensitized with gold and sulfur sensitizers, and further red Anhydrous 9-ethyl-3,3 as a sensitizing dye
'-G(3-sulfopropyl)-4,5,4ko5'-
Dibenzothiacarbocyanine hydroxide, anhydrous 5.5
'-dichloro-9-ethyl-3,37-di(3-sulfobutyl)thiacarbocyanine hydroxide; and anhydrous 2-(2-((5-chloro-3-ethyl-2(3H)
-penzothiazolidene)methyl)-1-butenyl-5-
After adding chloro-3-(4-sulfobutyl)benzoxacilium, 4-hydroxy-6-methyl-1,3
, 3a, 7'7-titrazaine 7' y 1.01 and 1-phenyl-5-mercaptotetrazole 10.
07V was added to prepare a red-sensitive emulsion. Furthermore, per mole of silver halide, 17 g of 1-hydroxy-N-(4-(2°4)-di-t-amylphenoxy)butyl]-2-naphthamide and 0.5.9 g of dodecyl galley) were added as cyan couplers. Addition of tricresyl phos 7A)
A mixture of 20.9 and 60 ethyl arsenate was heated and dissolved, and 1.5
A red-sensitive high-sensitivity emulsion was prepared by adding a 7.5% aqueous gelatin solution containing 11 to 30 hemp and emulsifying and dispersing it in a colloid mill, and coating it at a coating silver amount of 2.01/nl. 0 (Contains 160 g of gelatin per mole of silver halide.) 5th layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide as shown in Table 2 The emulsion was chemically sensitized with gold and sulfur sensitizers, respectively, and anhydrous 5,57-dichloro-9-ethyl-3°3'-di,(3-sulfobutyl)oxacarbocyanine hydroxide was added as a green-sensitive sensitizing dye. ;Anhydrous s, s
'-Diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide and anhydrous 9-ethyl 3,3'-di(3-sulfopropyl)
-5,6,s: Add 6'-dibenzoxacarbocyanine hydroxide followed by 1.0 g of 4-hydroxy-6-methyl 1,3,3ay7 tetrazaindene and 1
-Phenyl-5-mercaptotetrazole 20.0”&
It was prepared in the usual way. The two types of silver halide emulsions thus obtained were mixed at a ratio of 1:1 to prepare a green-sensitive and low-sensitivity silver halide emulsion.

In addition, 1 magenta coupler per mole of silver halide.
-(2,4,6-)dichlorophenyl)-3-13-(
2,4-di-t-amylphenoxy)acetamide)-
5-Virazolone 1oo11, %1-(2,4,6-)dichlorophenyl)- as colored magenta coupler
4-(1-naphthyl azo) -3-(2-10 rho 5-
Octadecenyl succinimide anilino)-5-pyrazolone 2.5. P, also dodecyl gallate 0.5.9.
DIR compounds as shown in Table 2 (1, tricresylphosphny) 120.9 and ethyl acetate 2
A mixture of 40IILt was dissolved by heating, added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the dispersion was emulsified and dispersed in a colloid mill to prepare an M-sensitive low-sensitivity emulsion. It was applied so that (Contains 160 g of gelatin per mole of silver halide.) Seventh layer: Green-sensitive and highly sensitive silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, containing 7 mole % of silver iodide). Chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3, as a green-sensitive sensitizing dye.
37-di(3-sulfobutyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide and anhydrous-9-ethyl-3 ,3'-
G(3-sulfopropyl' 5+ 6+ 5+
'6' ~ Add dibenzoxacarpodianine hydroxide and then 4-hydroxy-6-methyl-1,3,3a
, 1.0 g of 7-chitrazaindene and 10.0 g of 1-phenyl-5-mercaptotetrazole. , O, ~ were added to prepare a green-sensitive and highly sensitive silver halide emulsion. Furthermore, 1-(2,
4,6-trichlorophenyl)-3-(3-(2,4-
1-( di-t-amylphenoxy)acetamido)-5-pyrazolone 8011 as colored domase/takabra
2,4,6-)lichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolo 72.511.2
．． 5-di-t-octylhydroquinone 1.5II,
As DIR compounds, tricresyl 7 osphae) 120# and ethyl acetate 24 were added as shown in Table 2.
A green-sensitive high-sensitivity emulsion was prepared by heating and dissolving the 0 mt mixture, adding it to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and adding the dispersion that had been emulsified and dispersed in a colloid mill. ya''K. (halogen/(contains 160I gelatin per mole) S*: Intermediate layer Same as 2nd layer 9th layer: yellow filter 1 layer yellow 40I gelatin in which silver is dispersed K2 in aqueous solution
．． 5-G t-octylhydro Noa 311 and G 2
- ethylhexyl 7 thale) 1.51 ethyl acetate lOm
A dispersion of gelatin dissolved at t and dispersed in an aqueous gelatin solution containing 0.3II of sodium triisopropylnaphthalene sulfonate was added, and gelatin was added at 0.9ji/m.
5-di-t-octylhydroquinone o, 10Ji'/
It was applied so that the thickness was m.

1st O layer: Blue-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6μ, containing 6 mol% silver iodide)
was chemically sensitized with gold and sulfur sensitizers, and then anhydrous 5,5'-dimethoxy-3,3'-di(3
-Sulfopropyl)thiacyanine hydroxyto was added and then 4-hydroxy-6-methyl-1,3,3m, 7
Tetrazynde y1. o, 11-phenyl-5-mercaptotetrazole 20.019 was added thereto and prepared in a conventional manner to produce a blue-sensitive, low-sensitivity silver halide emulsion. Furthermore, α-pivaloyl-α-(1-benzyl-2-phenyl-3,5-
dioxo-1,2,4-)lyasiridin-4-yl)-
2'-chloro-57(α-(dodecyloxycarbonyl)ethoxycarbonyl)acetanilide 120.fl'
, α-(3-(α-(2,4-di-t-amylphenoxy)butyramide))benzoyl-27-medogycyacetanilide 50J7 and dibutyl 7 thale) 1
20.9. Heat and dissolve a mixture of 300 m6 of ethyl acetate, add it to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and add the dispersion emulsified in a colloid mill to prepare a blue-sensitive, low-sensitivity silver halide emulsion. The coating was carried out so that the coating silver amount was 0.79/rrl.

(Contains 16Q9 gelatin per mole of silver halide) No. 114: Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2μ, containing 7 mol% silver iodide)
was chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'-C (
3-sulfopropyl) thiacyanine hydroxide, then 4-hydroxy-6-methyl-1,3,3a,
7tetrazaindene 1.011 and 1-phenyl-
5-Mercaptotetrazole 1 (prepared in a conventional manner by adding 1101119 ~ blue-sensitive high-sensitivity silver halide compound'
A drug was prepared. Furthermore, α-pivaloyl-α-(1-bensyl-2
-Phenyl-3゜5-dioxo-1,2,4-triacylidin-4-yl)-2'-chloro-5'-[α-(dotecyloxycarbonyl]ethoxycarbonyl]acetanilide 80I was added and dibutyl 7-thale was added. )'80Ji
's ethyl acetate 240 rILt mixture was heated and dissolved, added to an aqueous gelatin solution containing sodium triimpropylnaphthalene sulfonate, and the dispersion emulsified and dispersed in a colloid mill was added to prepare a blue-sensitive, high-sensitivity silver halide emulsion. Then, coating was carried out so that the amount of coated silver was 0.9 IIm.

(Contains 240% gelatin per mole of silver halide) 12th layer: Intermediate layer 2g of di-2-ethylhexyl phthalate 2-[3-cyano-3-(n-dodecylamide 7carboxyl>7') )'
) -1-Ethylpyrrolidine 211, acetic acid, and 2 parts of ethyl pyrrolidine were mixed, and a dispersion of the mixture was dispersed in an aqueous gelatin solution containing 0.6 g of sodium triisopropylnaphthalene sulfonate. It was coated at a coating rate of .011/m.

13th layer: Protective layer 10 (gelatin aqueous solution containing 4F of gelatin and 0.2# of 1.2-bisvinylsulfonylethane per IJ was coated so that gelatin L was 31/rt?) Sample obtained in this way Regarding 14 to 24, similarly to Example 1,
Exposure and development were performed. Furthermore, the obtained dye image was evaluated in the same manner as in Example 1. The results obtained are shown in Table 2.

As is clear from Table 2, as in Example 1, the combination of the monodispersed emulsion of the present invention and the DIR compound greatly improved the instantaneous contact effect during development and the stability of the dye image over time in the multilayer sample. I can see that it has been improved.

Agent Umi Kuwa Hara

Claims (1)

[Claims] In a silver rogonide photographic light-sensitive material having at least one photosensitive silver rokenide emulsion layer on the support, the photosensitive silver roganide emulsion 1- is actually Contains monodisperse silver rokenide particles and a development inhibitor-releasing compound that releases a dust palpitation inhibitor and generates a mobile reaction product by reaction with an oxidized form of a color developing agent. It is characterized by the fact that... it is a ``logonization bride''.